EP0075755A2 - Pigments nacrés stables à la lumière, procédé de fabrication et utilisation - Google Patents

Pigments nacrés stables à la lumière, procédé de fabrication et utilisation Download PDF

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Publication number
EP0075755A2
EP0075755A2 EP82108245A EP82108245A EP0075755A2 EP 0075755 A2 EP0075755 A2 EP 0075755A2 EP 82108245 A EP82108245 A EP 82108245A EP 82108245 A EP82108245 A EP 82108245A EP 0075755 A2 EP0075755 A2 EP 0075755A2
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EP
European Patent Office
Prior art keywords
chromium
pigments
pigment
coated
mica
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP82108245A
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German (de)
English (en)
Other versions
EP0075755A3 (fr
Inventor
Horst Dr. Bernhard
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of EP0075755A2 publication Critical patent/EP0075755A2/fr
Publication of EP0075755A3 publication Critical patent/EP0075755A3/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/102—Interference pigments characterized by the core material the core consisting of glass or silicate material like mica or clays, e.g. kaolin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/301—Thickness of the core
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/302—Thickness of a layer with high refractive material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2210/00—Special effects or uses of interference pigments
    • C09C2210/20—Optical properties in the UV-range
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2220/00—Methods of preparing the interference pigments
    • C09C2220/10—Wet methods, e.g. co-precipitation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2220/00—Methods of preparing the interference pigments
    • C09C2220/10—Wet methods, e.g. co-precipitation
    • C09C2220/103—Wet methods, e.g. co-precipitation comprising a drying or calcination step after applying each layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2220/00—Methods of preparing the interference pigments
    • C09C2220/10—Wet methods, e.g. co-precipitation
    • C09C2220/106—Wet methods, e.g. co-precipitation comprising only a drying or calcination step of the finally coated pigment

Definitions

  • the invention relates to pearlescent pigments with a yellow powder color and improved light fastness on the basis of mica flakes coated with titanium dioxide, to which an additional coloring protective layer is applied.
  • the invention therefore relates to pearlescent pigments with a yellow powder color and improved light fastness on the basis of mica flakes coated with titanium dioxide, an additional coloring protective layer being applied to the titanium dioxide layer, characterized in that a thin layer of annealed chromium oxide and / or chromium phosphate is applied as the protective layer .
  • the invention also relates to a process for the preparation of these pigments and their use.
  • mica flakes are first coated in a customary manner with TiO 2 and optionally also other metal oxides.
  • These mica flake pigments used as base pigments are generally mica flakes with a diameter of approximately 5-200 ⁇ m and a thickness of approximately 0.1-5 ⁇ m, which are coated with a metal oxide layer.
  • metal oxide coatings to be due to the advantageous refractive index, titanium dioxide mainly or T itandioxidaquate and / or zirconium dioxide or used Zirkondioxidaquate. Together with these metal oxides, however, other colorless or optionally also colored metal oxides such as, for. B. SnO 2 , Al 2 O 3 or Fe 2 0 3 can be used.
  • a particularly frequently used pigment is e.g. B. a mica flake pigment in which mica flakes with a diameter of about 5 - 50 microns and a thickness of about 0.5 microns are evenly coated with a possibly hydrated titanium dioxide layer, the mica surface being a TiO 2 layer of about 50 - 500 mg TiO 2 per m 2 .
  • These pearlescent pigments have different interference colors depending on the layer thickness of the precipitated metal oxide layer. All of these pigments are known and e.g. B. in the German patents and patent applications N r. 1467468, 1959998, 2009566, 2060850, 2106613, 2214545, 2215191 and 2522572. Pigments with a yellow interference color are particularly preferred. In these cases, aftertreatment with chromium compounds leads to brilliant gold pigments, which stand out extremely advantageously from the previously known iron oxide-containing reddish gold pigments due to the clear shade.
  • the base pigments are products that are calcined at higher temperatures of around 600 - 1000 ° C.
  • the chromium (III) layer is applied directly after the mica has been coated with the other metal oxides and only then is it annealed.
  • pigments are obtained which differ advantageously from those of the prior art, but generally not quite the quality of the two-time coating, i.e. after the metal oxide coating and after the coating with chromium (III), reach annealed pigments.
  • the pigments produced by this process which can be carried out in one step and are therefore inexpensive, are completely sufficient for certain applications and are therefore preferred for these applications. It is crucial in any case that the pigment is annealed after coating with the chromium (III) compound.
  • Particularly preferred base pigments are the rutile / mica pigments known from German Offenlegungsschrift 2522572, which have a layer structure, with a thin TiO 2 layer and then at least the sequence SnO 2 / TiO 2 alternatingly striking the mica surface, which subsequently occurs a temperature up to about 1000 0 C are annealed.
  • these preparations can also be used uncalcined. The rutile structure then arises when the products coated with the sparingly soluble chromium compound are annealed.
  • the base pigment which has the desired interference color, is suspended in aqueous solution and mixed with chromium hydroxide and / or coated with chromium phosphate.
  • the conditions for the coating can be varied within a wide range. All that is desired is that the sparingly soluble chromium (III) compound formed in the suspension by chemical reaction, hydrolysis or reduction is formed only in such an amount that it can be continuously deposited on the pigment surface without it forming substantial amounts comes from free precipitation particles in the suspension.
  • the difficultly soluble chromium (III) compound can be formed both from chromium (III) salts and from chromium (VI) compounds.
  • the pigment suspension can contain the ions (hydroxyl and / or phosphate ions) necessary for the precipitation, with a chromium (III) salt solution being allowed to run in slowly, or a chromium (IIII salt) containing pigment suspension slowly with hydroxyl and / or phosphate ions, but it is also possible to add both a chromium salt solution and a solution containing the precipitating ions to the pigment suspension at the same time, as a rule maintaining a constant pH value, or in the chromium salt-containing pigment suspension by chemical reaction, such as homogeneous hydrolysis, the ions necessary for the precipitation are formed.
  • Chromium (III) ions can, however, also be formed in situ from chromium (VI) compounds.
  • a chromium (VI) salt solution in the pigment suspension with a reducing agent such as. B. hydrazine or hydroxylamine. mixed, either one component being added and the other being added, or both components being slowly added to the pigment suspension at the same time.
  • the pH in the pigment suspension should be above about 3, with values of between 4.5 and 9 being preferred. Any base per se can be used to adjust the pH, which would be in the strongly acidic range if only the acidic chromium (III) salt solution were added. Examples include: ammonia (in solution or gaseous), sodium hydroxide solution or potassium hydroxide solution. Ammonia is preferably used.
  • any soluble chromium (III) salt or chromate (VI) per se can be used to supply chromium (III) ions. CrCl 3 or chromium alum solutions or potassium dichromate are preferably used. If phosphate precipitation is to take place, both orthophosphoric acid and its primary, secondary and tertiary salts and polymeric phosphates can be used. In addition to phosphoric acid, z. B. KH 2 P0 4 , Na 2 HPO 4 x 12 H 2 O, Na 3 PO 4 x 12 H 2 0, Na 4 P 2 O 7 x 7H 2 O and (NaP0 3 ) x '
  • the precipitation itself can be carried out at any temperature between the freezing and boiling point of the slurry. However, it has been shown that secondary precipitation can occur at relatively low temperatures. It is therefore preferred at elevated temperature, e.g. B. worked about 50 - 100 ° C, especially about 50 - 90 ° C. However, good quality precipitation is generally also achieved at other temperatures.
  • chromium hydroxide or chromium phosphate precipitate be formed on the pigment particles.
  • Mixtures of chromium hydroxide and chromium phosphate with one another as well as mixtures with other, preferably colorless, metal oxides can be applied, which are applied either simultaneously with the chromium compound or in a thin layer before or after.
  • a chromium hydroxide precipitate can be partially or completely converted into chromium phosphate by treating the pigment particles coated therewith with phosphate-containing solutions without the coating losing effectiveness.
  • Relatively small amounts of the chromium compound are sufficient to achieve the improvement in light fastness according to the invention.
  • the full stabilizing effect can be demonstrated even at a content of 0.5% by weight (calculated as Cr 2 0 3 and based on the total pigment).
  • Cr 2 0 3 the content of 0.5% by weight
  • the chromium content is above about 4% by weight, not all of the chromium can be reacted with titanium dioxide to give the yellow chromium titanate.
  • the pigments according to the invention therefore preferably have a content of approximately 0.2-3% by weight of the chromium compound, calculated as Cr203.
  • the pigments After coating the base pigments with chromium hydroxide and / or chromium phosphate, the pigments are processed in the usual way. As a rule, they are filtered off, washed and dried. In contrast to the known aftertreatment by coating with chromium hydroxide, however, calcination at temperatures of about 500 to about 1000 ° C. then preferably follows about 700 to about 900 ° C. In this calcination, which is usually carried out for about half an hour to an hour, any chromium hydroxide and other hydroxides and aquates present are dewatered and the brilliant yellow pigment color is formed by reaction with the Ti0 2 .
  • the pigments thus obtained have has an attractive G Oldton relation to those produced by the prior art, not annealed pigments markedly improved light fastness, so that by the invention new valuable pigments are obtained.
  • the pigments according to the invention can be used in the same way as those known hitherto. B. as an additive to plastics, paints or varnishes, but in particular also in personal care products and cosmetics. Due to the improved light fastness, all applications in which the pigments are exposed to environmental influences are preferred, in particular, for. B. in car paints.
  • 120 g of a mica pigment coated with alternating layers of TiO 2 / SnO 2 / TiO 2 / SnO 2 / TiO 2 using the method of DOS 2522572 and then annealed at 900 ° C with a yellow interference color (platelet size 10 to 60 ⁇ m, mica content 50.8 %, Ti0 2 content 42.2%, SnO 2 content 7.0%) are slurried in 2.4 l of water and heated to 75 ° C.
  • the suspension is adjusted to pH 6.0 with 5% ammonia solution and within 15 minutes with a solution of 0.8 g KCr (S0 4 ) 2 . 12 H 2 0 in 30 ml of water, the pH being kept constant by the simultaneous addition of 5% ammonia solution.
  • the same base pigment is coated with such amounts of chromium hydroxide that a Cr 2 0 3 content of 0.5, 1.0, 4.0 and 8% results after the annealing.
  • a weathering test in which the pigments incorporated in PVC are exposed to high moisture and UV light, shows that the pigments coated with 0.1% Cr 2 O 3 already show less discoloration than the base pigments and that already With a Cr203 content of 0.5%, discoloration can hardly be detected.
  • the products with a Cr 2 0 3 content from 4% already have a clear green tone.
  • a suspension of 120 g of the base pigment from Example 1 in 2.4 l of water is heated to 75 ° C., adjusted to pH 6.2 with 5% ammonia solution and slowly with a solution of 4.0 g of KCr (S0 4 ) . 12 H 2 0 in 50 ml of water, the pH being kept constant by simultaneous addition of 5% ammonia. After stirring for 30 minutes, half of the suspension is filtered off, washed, dried and calcined at 840 ° C. for 30 minutes. A solution of 1.5 g of Na 2 HPO 4 .12 H 2 0 in 100 ml of water is added to the second half of the suspension and after 30 minutes it is filtered off, washed, dried and annealed at 840 ° C. for 30 minutes. Both preparations show a lively G oldglanz and contain about 0.5% Cr203.
  • potassium mica with a platelet size of 5 to 200 ⁇ m at 75 ° C and a pH of 1 to 2.5 is first coated with a TiO 2 layer of 5 nm thick, then with a SnO 2 -Layer of 5 - 10 nm thickness, a TiO 2 layer of 45 - 55 nm, again a SnO 2 layer of about 5 nm and then coated with Ti0 2 until a yellow interference color is reached.
  • the pH is then adjusted to about 6 and both a chromium (III) chloride solution and an ammonia solution are slowly added at the same time, as a result of which the pH is kept largely constant at 6.
  • chromium hydroxide layer which corresponds to about 0.1% by weight of chromium oxide, based on the total pigment, is noticeable
  • the pigment is filtered off, washed, dried and annealed at 800 ° C. for 0.5 hour.
  • the same base pigment is coated with such amounts of chromium hydroxide that a Cr 2 0 3 content of 0.5, 1.0, 4.0 and 8% results after the annealing.
  • a weathering test in which the pigments incorporated into PVC are exposed to high moisture and UV light, shows that the pigments coated with 0.1% Cr 2 O 3 already show less discoloration than the base pigments, and that they do with a Cr 2 0 3 content of 0.5%, discoloration can hardly be detected.
  • the products with a Cr 2 0 3 content from 4% already have a clear green tone.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Cosmetics (AREA)
  • Paints Or Removers (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
EP82108245A 1981-09-23 1982-09-08 Pigments nacrés stables à la lumière, procédé de fabrication et utilisation Withdrawn EP0075755A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3137808 1981-09-23
DE19813137808 DE3137808A1 (de) 1981-09-23 1981-09-23 Perlglanzpigmente mit verbesserter lichtechtheit, verfahren zur herstellung und verwendung

Publications (2)

Publication Number Publication Date
EP0075755A2 true EP0075755A2 (fr) 1983-04-06
EP0075755A3 EP0075755A3 (fr) 1983-07-20

Family

ID=6142390

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82108245A Withdrawn EP0075755A3 (fr) 1981-09-23 1982-09-08 Pigments nacrés stables à la lumière, procédé de fabrication et utilisation

Country Status (10)

Country Link
US (1) US4456486A (fr)
EP (1) EP0075755A3 (fr)
JP (1) JPS5869258A (fr)
BR (1) BR8205542A (fr)
CA (1) CA1184003A (fr)
CS (1) CS233732B2 (fr)
DE (1) DE3137808A1 (fr)
ES (1) ES515883A0 (fr)
IN (1) IN157834B (fr)
ZA (1) ZA826930B (fr)

Cited By (5)

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EP0177637A1 (fr) * 1983-06-18 1986-04-16 Wanfried-Druck Kalden GmbH Procédé de bronzage d'imprimés polychromes traités avec un mordant
EP0186607A1 (fr) * 1984-12-11 1986-07-02 Basf Corporation Peinture multicouche à fini satiné pour voitures
EP0298604A2 (fr) * 1987-07-06 1989-01-11 The Mearl Corporation Objets décoratifs présentant des effets multicolores
EP0657510A2 (fr) * 1993-12-06 1995-06-14 The Mearl Corporation Pigments micacés revêtus de dioxyde de titane de forme rutile préparés sans étain
EP0757085A3 (fr) * 1995-08-04 1998-06-03 MERCK PATENT GmbH Pigment à effet de nacre et procédé pour le produire

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JPS6067407A (ja) * 1983-09-22 1985-04-17 Pola Chem Ind Inc メ−クアツプ化粧料
DE3334598A1 (de) * 1983-09-24 1985-04-18 Merck Patent Gmbh Witterungsbestaendige perlglanzpigmente
JPS61225264A (ja) * 1985-03-29 1986-10-07 Shiseido Co Ltd 有色真珠光沢塗料
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JP2691400B2 (ja) * 1987-03-18 1997-12-17 テイカ 株式会社 二酸化チタン被覆酸化鉄顔料
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DE19951869A1 (de) 1999-10-28 2001-05-03 Merck Patent Gmbh Farbstarke Interferenzpigmente
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DE10029648C1 (de) 2000-06-15 2002-02-07 Goldschmidt Ag Th Blockcopolymere Phosphorsäureester, deren Salze und deren Verwendung als Emulgatoren und Dispergiermittel
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FR2844448B1 (fr) * 2002-09-17 2006-06-23 Lcw Les Colorants Wackherr Methode de preparation extemporanee de compositions cosmetiques ayant la texture d'une creme, et compositions pour la mise en oeuvre de cette methode
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DE10310736A1 (de) 2003-03-10 2004-09-23 Merck Patent Gmbh Interferenzpigmente mit Körperfarbe
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EP0177637A1 (fr) * 1983-06-18 1986-04-16 Wanfried-Druck Kalden GmbH Procédé de bronzage d'imprimés polychromes traités avec un mordant
EP0186607A1 (fr) * 1984-12-11 1986-07-02 Basf Corporation Peinture multicouche à fini satiné pour voitures
EP0298604A2 (fr) * 1987-07-06 1989-01-11 The Mearl Corporation Objets décoratifs présentant des effets multicolores
EP0298604A3 (en) * 1987-07-06 1990-10-10 The Mearl Corporation Decorative objects with multicolor effects
EP0657510A2 (fr) * 1993-12-06 1995-06-14 The Mearl Corporation Pigments micacés revêtus de dioxyde de titane de forme rutile préparés sans étain
EP0657510A3 (fr) * 1993-12-06 1996-02-07 Mearl Corp Pigments micacés revêtus de dioxyde de titane de forme rutile préparés sans étain.
EP0757085A3 (fr) * 1995-08-04 1998-06-03 MERCK PATENT GmbH Pigment à effet de nacre et procédé pour le produire

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IN157834B (fr) 1986-07-05
JPS5869258A (ja) 1983-04-25
CA1184003A (fr) 1985-03-19
US4456486A (en) 1984-06-26
ES8306497A1 (es) 1983-06-01
EP0075755A3 (fr) 1983-07-20
ZA826930B (en) 1983-11-30
CS233732B2 (en) 1985-03-14
ES515883A0 (es) 1983-06-01
BR8205542A (pt) 1983-08-30
DE3137808A1 (de) 1983-03-31

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